CN108483404A - A kind of preparation method of unformed metal hydroxides nanometer sheet and phosphide nanometer sheet - Google Patents
A kind of preparation method of unformed metal hydroxides nanometer sheet and phosphide nanometer sheet Download PDFInfo
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- CN108483404A CN108483404A CN201810358877.6A CN201810358877A CN108483404A CN 108483404 A CN108483404 A CN 108483404A CN 201810358877 A CN201810358877 A CN 201810358877A CN 108483404 A CN108483404 A CN 108483404A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
The present invention provides a kind of preparation methods of unformed metal hydroxides nanometer sheet and phosphide nanometer sheet.The present invention is using one-dimensional hard calcium silicate nanowire as mould material, and using soluble metallic salt as source metal, unformed metal hydroxides nanometer sheet can be synthesized after water-bath.Wherein calcium silicate nanowire is in composite inner, and unformed metal hydroxides nanometer sheet is in outside, forms the growth model similar to hydrotalcite.In addition, metal phosphide nanometer sheet can be prepared by further phosphatization on the basis of unformed metal hydroxides nanometer sheet.Products therefrom form is uniform.The present invention's is not necessarily to complex device, and preparation process is easy to operate, mild condition, is easy to magnanimity preparation, raw material sources are extensive, are conducive to the realization of industrialized production.Prepared unformed metal hydroxides nanometer sheet and metal phosphide nanometer sheet has very extensive application prospect in photoelectrocatalysis, energy storage, the fields such as photodetection.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of unformed metal hydroxides nanometer sheet and
The preparation method of phosphide nanometer sheet.
Background technology
Since graphene in 2004 is found, two-dimension nano materials cause researchers and greatly pay close attention to.
Scientists have prepared a variety of ultra-thin two-dimension materials, including metal hydroxides, gold in nearest many decades
Belong to oxide, hexagonal boron nitride (h-BN), Transition-metal dichalcogenide, graphitic nitralloy carbon (g-C3N4) and black squama etc..These materials
Material has similar two-dimensional sheet structure with graphene, has high-specific surface area and atomic-level thickness, nanometer sheet surface abundant
Defect sturcture is that research catalysis and the relationship at active end create an extraordinary platform.
Wherein, in electro-catalysis, the fields such as lithium ion battery and ultracapacitor are equal for metal hydroxides and metal phosphide
It has potential application, has received the extensive concern of researcher.Research surface before, the crystalline state meeting of hydroxide
Its electro-chemical activity is influenced, the electrochemical properties of unformed hydroxide are more preferable than the hydroxide of crystallization, this is because without fixed
Type substance has smaller volume expansion and more faults of construction.
Therefore develop that a kind of raw material sources are extensive, the mild condition and simple controllable unformed metal hydroxides of method is received
The universal synthesis method of rice piece and metal phosphide nanometer sheet, realizes large-scale industrial production, has very great meaning
Justice.
Invention content
In view of this, the technical problem to be solved in the present invention be to provide a kind of unformed metal hydroxides nanometer sheet and
Phosphide nanometer sheet and preparation method thereof, of the invention is not necessarily to complex device, and preparation process is easy to operate, and mild condition is easy to
Prepared by magnanimity, raw material sources are extensive, are conducive to the realization of industrialized production.Prepared unformed metal hydroxides nanometer
Piece and metal phosphide nanometer sheet are in photoelectrocatalysis, and energy storage, the fields such as photodetection have very extensive application prospect.
The present invention provides a kind of preparation methods of unformed metal hydroxides nanometer sheet, include the following steps：
A) aqueous dispersions of calcium silicate nanowire and soluble metal source compound are mixed, obtain mixed solution；
B the mixed solution) is subjected to water-bath, obtains unformed metal hydroxides nanometer sheet.
The present invention also provides a kind of preparation methods of phosphide nanometer sheet, include the following steps：
A) aqueous dispersions of calcium silicate nanowire and soluble metal source compound are mixed, obtain mixed solution；
B) mixed solution is subjected to water-bath, obtains unformed metal hydroxides nanometer sheet；
C) it by the unformed metal hydroxides nanometer sheet and dihydrogen phosphite salt, is carried out under the conditions of protective atmosphere high
Temperature calcining, obtains phosphide nanometer sheet.
Preferably, the calcium silicate nanowire is prepared as follows：
I) aqueous solution of soluble calcium salt is mixed with mensuration dissolubility silicic saline solution, is reacted, obtain suspension；
Ii the suspension) is subjected to heating reaction in confined conditions, obtains reaction product；
Iii it is freeze-dried after) washing the reaction product, obtains calcium silicate nanowire powder.
Preferably, the soluble calcium salt is one or more in calcium nitrate and calcium halide；The soluble calcium salt
Aqueous solution a concentration of 0.1~1.0mol/L；
The soluble silicate is selected from sodium metasilicate, a concentration of 0.1~1.0mol/ of the mensuration dissolubility silicic saline solution
L；
The molar ratio of calcium in the soluble calcium salt and the silicon in the soluble silicate is (0.1~10)：1.
Preferably, in step i), the time of the mixing is 0.5~5h；
Step ii) in, the temperature of the heating reaction is 100~220 DEG C, and the reaction time is 1~30h；
Step iii) in, it washs to be washed respectively using water and ethyl alcohol, uses water washing number for 1~5 time, use
The number of ethyl alcohol washing is 1~5 time.
Preferably, the mass fraction of the aqueous dispersions of the calcium silicate nanowire is 0.01wt%~10wt%；Wherein, often
The amount of the soluble metal source compound mixed in the aqueous dispersions of the calcium silicate nanowire of 20~200ml be 1.0mmol~
10.0mmol。
Preferably, the bath temperature be 20~100 DEG C, water bath time be 1~for 24 hours.
Preferably, the soluble metal source compound be selected from soluble metal nitrate, soluble metal halide, can
It is one or more in solube metallic sulfate and soluble metal acetate.
Metallic element in the soluble metal source compound includes group VIII metal element, IV B races metallic element, V
It is one or more in B races metallic element, VI B races metallic element, VII B race's metallic elements and Group IIB metal element.
Preferably, the dihydrogen phosphite salt is selected from sodium dihydrogen phosphite or potassium dihydrogen phosphite, the unformed metal
The mass ratio of hydroxide nano piece and dihydrogen phosphite salt is (10~500)：(1~100).
Preferably, the protective atmosphere condition is selected from nitrogen or argon gas, and the temperature of the high-temperature calcination is 100~900 DEG C,
Time is 1~10h, and calcining heating rate is 0.1~10 DEG C/min.
Compared with prior art, the present invention provides a kind of preparation method of unformed metal hydroxides nanometer sheet, packets
Include following steps：A) aqueous dispersions of calcium silicate nanowire and soluble metal source compound are mixed, obtain mixing molten
Liquid；B the mixed solution) is subjected to water-bath, obtains unformed metal hydroxides nanometer sheet.The present invention also provides one
The preparation method of kind phosphide nanometer sheet, includes the following steps：A) by the aqueous dispersions of calcium silicate nanowire and soluble metal
Source compound is mixed, and obtains mixed solution；B) mixed solution is subjected to water-bath, obtains unformed metal hydrogen-oxygen
Compound nanometer sheet；C) by the unformed metal hydroxides nanometer sheet and dihydrogen phosphite salt, under the conditions of protective atmosphere into
Row high-temperature calcination obtains phosphide nanometer sheet.
The present invention is using one-dimensional hard calcium silicate nanowire as mould material, anti-in water-bath using soluble metallic salt as source metal
Unformed metal hydroxides nanometer sheet can be synthesized after answering.Wherein calcium silicate nanowire is in composite inner, unformed
Metal hydroxides nanometer sheet is in outside, forms the growth model similar to hydrotalcite.In addition, in unformed metal hydrogen-oxygen
Metal phosphide nanometer sheet can be prepared by further phosphatization on the basis of compound nanometer sheet.Products therefrom form is uniform.
The present invention's is not necessarily to complex device, and preparation process is easy to operate, mild condition, is easy to magnanimity preparation, raw material sources are extensive, favorably
In the realization of industrialized production.Prepared unformed metal hydroxides nanometer sheet and metal phosphide nanometer sheet are in photoelectricity
Catalysis, energy storage, the fields such as photodetection have very extensive application prospect.
Description of the drawings
Fig. 1 is the hard calcium silicate nanowire transmission electron microscope picture prepared in embodiment 1；
Fig. 2 is the unformed Co (OH) prepared by the induction of hard calcium silicate nanowire in embodiment 12The transmission electricity of nanometer sheet
Mirror picture；
Fig. 3 is unformed Co (OH) in embodiment 12Transmission electron microscope picture after nanometer sheet phosphatization；
Fig. 4 is the unformed Ni (OH) prepared by the induction of hard calcium silicate nanowire in embodiment 22The transmission electricity of nanometer sheet
Mirror picture；
Fig. 5 is the unformed Zn (OH) prepared by the induction of hard calcium silicate nanowire in embodiment 32The transmission electricity of nanometer sheet
Mirror picture；
Fig. 6 is the unformed Co prepared by the induction of hard calcium silicate nanowire in embodiment 60.5Ni0.5(OH)2Nanometer sheet
Transmission electron microscope picture；
Fig. 7 is unformed Co in embodiment 40.5Ni0.5(OH)2The cobalt nickel phosphide nanometer sheet prepared after nanometer sheet phosphatization
Transmission electron microscope picture；
Fig. 8 is unformed Co in embodiment 40.5Ni0.5(OH)2The cobalt nickel phosphide nanometer sheet prepared after nanometer sheet phosphatization
Scanning electron microscopic picture；
Fig. 9 is unformed Co in embodiment 40.5Ni0.5(OH)2The cobalt nickel phosphide nanometer sheet prepared after nanometer sheet phosphatization
The LSV curves of electrolysis water evolving hydrogen reaction (HER)；
Figure 10 is the unformed Co prepared by the induction of hard calcium silicate nanowire in embodiment 50.33Ni0.33Mn0.33(OH)2
Nanometer sheet transmission electron microscope picture.
Specific implementation mode
The present invention provides a kind of preparation methods of unformed metal hydroxides nanometer sheet, include the following steps：
A) aqueous dispersions of calcium silicate nanowire and soluble metal source compound are mixed, obtain mixed solution；
B the mixed solution) is subjected to water-bath, obtains unformed metal hydroxides nanometer sheet.
The present invention is using calcium silicate nanowire as mould material, wherein the calcium silicate nanowire carries out as follows
It prepares：
I) aqueous solution of soluble calcium salt is mixed with mensuration dissolubility silicic saline solution, is reacted, obtain suspension；
Ii the suspension) is subjected to heating reaction in confined conditions, obtains reaction product；
Iii it is freeze-dried after) washing the reaction product, obtains calcium silicate nanowire powder.
When carrying out calcium silicate nanowire preparation, the aqueous solution of soluble calcium salt and mensuration dissolubility silicic saline solution first is mixed
It closes, is reacted, obtain suspension；
The soluble calcium salt is one or more in calcium nitrate and calcium halide, preferably four water-calcium nitrate；It is described
A concentration of 0.1~1.0mol/L of the aqueous solution of soluble calcium salt, preferably 0.2~0.8mol/L, more preferably 0.5~
0.6mol/L；
The soluble silicate is selected from sodium metasilicate, more preferably nine water sodium metasilicate, the mensuration dissolubility silicic saline solution
A concentration of 0.1~1.0mol/L, preferably 0.2~0.8mol/L, more preferably 0.5~0.6mol/L；
The molar ratio of calcium in the soluble calcium salt and the silicon in the soluble silicate is (0.1~10)：1, it is excellent
It is selected as (0.5~8)：1, more preferably (1~2)：1.
The mode that the present invention mixes the aqueous solution of soluble calcium salt with mensuration dissolubility silicic saline solution preferably will be solvable
The aqueous solution of property calcium salt is added dropwise in mensuration dissolubility silicic saline solution, is stirred continuously, is obtained white suspension.Wherein, mixing
Temperature is preferably room temperature condition, in the present invention, the room temperature is defined as 25 ± 5 DEG C.The time of the mixing be 0.5~
5h, preferably 1~2h.
After obtaining suspension, the suspension is subjected to heating reaction in confined conditions, obtains reaction product.
Heating reaction is carried out in the present invention, it is preferred to which suspension is placed in Teflon stainless steel high temperature reaction kettles, it is described
The volume of stainless steel cauldron is 25mL~500mL, and optimal is 50mL；The temperature of the heating reaction is 100~220 DEG C, excellent
It is selected as 180~200 DEG C, the reaction time is 1~30h, preferably 20~24 hours.
Heating after reaction, obtains reaction product, the reaction product is separated by solid-liquid separation, solid product is washed
After be freeze-dried, obtain calcium silicate nanowire powder.
Washing is used water washing number for 1~5 time, preferably 3 times, used to be washed respectively using water and ethyl alcohol
The number of ethyl alcohol washing is 1~5 time, preferably 3 times.
The present invention is using soluble metal source compound as source metal, wherein the soluble metal source compound is selected from can
Solube metallic nitrate, soluble metal halide, soluble metal sulfate and one kind in soluble metal acetate or
It is a variety of；Metallic element in the soluble metal source compound includes group VIII metal element, IV B races metallic element, V B
It is one or more in race's metallic element, group vib metallic element, VII B race's metallic elements and Group IIB metal element.In this hair
In bright, the soluble metal source compound is preferably soluble chloride, more preferably iron chloride, cobalt chloride, nickel chloride, chlorine
Change zinc, it is one or more in manganese chloride.
The aqueous dispersions of calcium silicate nanowire and soluble metal source compound are mixed the present invention, obtain mixing molten
Liquid.
Wherein, the mode of mixing is：
Soluble metal source compound is added into the aqueous dispersions of calcium silicate nanowire, magnetic agitation is carried out, until
Solution went clear obtains mixed solution.
The mass fraction of the aqueous dispersions of the calcium silicate nanowire is 0.01wt%~10wt%, preferably 0.05wt%
~5wt%, more preferably 0.1wt%~3wt%；Wherein, it is mixed in the aqueous dispersions of the calcium silicate nanowire of every 20~200ml
Soluble metal source compound amount be 1.0mmol~10.0mmol, preferably 2.0~6.0mmol, more preferably 3.0~
5.0mmol.In certain specific embodiments of the invention, the water of the calcium silicate nanowire of a concentration of 0.1wt% per 50ml
The amount of the soluble metal source compound mixed in dispersion liquid is 3.0mmol.
The mixed solution is subjected to water-bath, obtains unformed metal hydroxides nanometer sheet
Wherein, the bath temperature is 20~100 DEG C, preferably 70~90 DEG C, more preferably 80 DEG C；The water bath time
For 1~for 24 hours, preferably 2~4 hours, preferably 3 hours.
After water-bath, room temperature cooling；Unformed metal hydroxides will be obtained after the washing drying of obtained product
Nanometer sheet powder.
The present invention also provides a kind of preparation methods of phosphide nanometer sheet, include the following steps：
A) aqueous dispersions of calcium silicate nanowire and soluble metal source compound are mixed, obtain mixed solution；
B) mixed solution is subjected to water-bath, obtains unformed metal hydroxides nanometer sheet；
C) it by the unformed metal hydroxides nanometer sheet and dihydrogen phosphite salt, is carried out under the conditions of protective atmosphere high
Temperature calcining, obtains phosphide nanometer sheet.
The present invention can prepare metal on the basis of unformed metal hydroxides nanometer sheet by further phosphatization
Phosphide nanometer sheet
Wherein, the preparation of unformed metal hydroxides nanometer sheet, i.e. step a) and step b) as described above, herein not
It repeats.
By obtained unformed metal hydroxides nanometer sheet and dihydrogen phosphite salt, carried out under the conditions of protective atmosphere high
Temperature calcining, obtains phosphide nanometer sheet.
Specifically, dihydrogen phosphite salt and unformed metal hydroxides nanometer sheet are respectively placed in small porcelain boat end to end
Place.I.e. dihydrogen phosphite salt is placed in the inlet of protective atmosphere air-flow, and unformed metal hydroxides nanometer sheet is placed in protection gas
The exit of atmosphere air-flow.
The dihydrogen phosphite salt is selected from sodium dihydrogen phosphite or potassium dihydrogen phosphite, preferably sodium dihydrogen phosphite, institute
The mass ratio for stating unformed metal hydroxides nanometer sheet and dihydrogen phosphite salt is (10~500)：(1~100), preferably
10:100。
The protective atmosphere condition is selected from nitrogen or argon gas, and the temperature of the high-temperature calcination is 100~900 DEG C, preferably
200~400 DEG C, more preferably 300 DEG C, time are 1~10h, preferably 2~4 hours, more preferably 3 hours；Calcining heating speed
Rate is 0.1~10 DEG C/min, preferably 0.4~1 DEG C/min, more preferably 0.5 DEG C/min.
The present invention is using one-dimensional hard calcium silicate nanowire as mould material, anti-in water-bath using soluble metallic salt as source metal
Unformed metal hydroxides nanometer sheet can be synthesized after answering.Wherein calcium silicate nanowire is in composite inner, unformed
Metal hydroxides nanometer sheet is in outside, forms the growth model similar to hydrotalcite.In addition, in unformed metal hydrogen-oxygen
Metal phosphide nanometer sheet can be prepared by further phosphatization on the basis of compound nanometer sheet.Products therefrom form is uniform.
The present invention's is not necessarily to complex device, and preparation process is easy to operate, mild condition, is easy to magnanimity preparation, raw material sources are extensive, favorably
In the realization of industrialized production.Prepared unformed metal hydroxides nanometer sheet and metal phosphide nanometer sheet are in photoelectricity
Catalysis, energy storage, the fields such as photodetection have very extensive application prospect.
For a further understanding of the present invention, unformed metal hydroxides provided by the invention is received with reference to embodiment
The preparation method of rice piece and phosphide nanometer sheet illustrates, and protection scope of the present invention is not limited by the following examples.
Drug and reagent used are purchased from Sinopharm Chemical Reagent Co., Ltd., hydro-thermal confined reaction in wherein testing
Container is the stainless steel cauldron of Fujian Sheng Xin Machinery Co., Ltd.s production.
Embodiment 1
1, the synthesis of hard calcium silicate nanowire
It weighs 0.2360g four water-calcium nitrates and nine water sodium metasilicate of 0.2840g is dissolved in respectively in 25mL ultra-pure waters, in room temperature
Under, calcium nitrate solution is added dropwise in sodium silicate solution, and continuous magnetic agitation, finally obtains white suspension；Then
Obtained white suspension is transferred in being reacted in Teflon stainless steel high temperature reaction kettles, 200 DEG C are reacted for 24 hours, obtained production
Object water and ethyl alcohol are washed 3 times respectively, and then freeze drying example, obtains white powder.
The hard calcium silicate nanowire prepared to the embodiment of the present invention 1 characterizes, and is the embodiment of the present invention referring to Fig. 1, Fig. 1
The transmission electron microscope photo of the 1 hard calcium silicate nanowire prepared, the diameter of hard calcium silicate nanowire is in 10-50nm as seen from the figure
Between, form is all very uniform.
2, hard calcium silicate nanowire induction prepares unformed Co (OH)2Nanometer sheet
The hard calcium silicates white powder of preparation is configured to the hard calcium silicate nanowire dispersion liquid of 0.1wt%, by 3mmol's
Cobalt nitrate hexahydrate is added to the hard calcium silicate nanowire of 50mL and adheres to separately in liquid, and wherein metal ion or metal ion mixture be most
Final concentration of 0.06mol/L, magnetic agitation 0.5h are until solution went clear, 80 DEG C of water-bath 3h, room temperature cooling, the production of acquisition
Object is washed with water 3 times, and ethyl alcohol is washed 1 time, the dry 6h in 60 DEG C of vacuum drying chambers.
Unformed Co (OH) prepared by the embodiment of the present invention 12Nanometer sheet is characterized.
Referring to Fig. 2, Fig. 2 is unformed Co (OH) prepared by the embodiment of the present invention 12The transmission electron microscope photo of nanometer sheet, by
Figure is it can be seen that the unformed Co (OH) prepared2Nanometer sheet is grown in calcium silicate nanowire surface, the size of nanometer sheet 50~
100nm or so, and be distributed than more uniform.
3, prepared by phosphatization cobalt nanometer sheet
Weigh the Co (OH) of 100mg dihydrogen phosphites and sodium 10mg2Nanometer sheet powder, be individually placed to small porcelain boat head and
Tail.Small porcelain boat is placed in quartz ampoule, is passed through argon gas, sodium dihydrogen phosphite is close to air inlet, with the heating rate of 0.5 DEG C/min
Temperature is raised to 300 DEG C, constant temperature 3h, after cooled to room temperature, obtains phosphatization cobalt nanometer sheet.
The phosphatization cobalt nanometer sheet prepared to the embodiment of the present invention 1 characterizes.
Referring to Fig. 3, Fig. 3 is the transmission electron microscope photo of phosphatization cobalt nanometer sheet prepared by the embodiment of the present invention 2, can be seen by figure
The nickel cobalt phosphide nanometer sheet for going out preparation is grown in calcium silicate nanowire surface, the size of nanometer sheet in 50~100nm or so, and
And distribution, than more uniform, pattern does not change after phosphatization.
Embodiment 2
1, the synthesis of hard calcium silicate nanowire
It weighs 0.2360g four water-calcium nitrates and nine water sodium metasilicate of 0.2840g is dissolved in respectively in 25mL ultra-pure waters, in room temperature
Under, calcium nitrate solution is added dropwise in sodium silicate solution, and continuous magnetic agitation, finally obtains white suspension；Then
Obtained white suspension is transferred in being reacted in Teflon stainless steel high temperature reaction kettles, 200 DEG C are reacted for 24 hours, obtained production
Object water and ethyl alcohol are washed 3 times respectively, and then freeze drying example, obtains white powder.
2, hard calcium silicate nanowire induction prepares unformed Ni (OH)2Nanometer sheet
The hard calcium silicates white powder of preparation is configured to the hard calcium silicate nanowire dispersion liquid of 0.1wt%, by 3mmol's
Six water nickel chlorides are added to the hard calcium silicate nanowire of 50mL and adhere to separately in liquid, and wherein metal ion or metal ion mixture be most
Final concentration of 0.06mol/L, magnetic agitation 0.5h are until solution went clear, 80 DEG C of water-bath 3h, room temperature cooling, the production of acquisition
Object is washed with water 3 times, and ethyl alcohol is washed 1 time, the dry 6h in 60 DEG C of vacuum drying chambers.
Unformed Ni (OH) prepared by the embodiment of the present invention 22Nanometer sheet is characterized.
Referring to Fig. 4, Fig. 4 is unformed Ni (OH) prepared by the embodiment of the present invention 32The stereoscan photograph of nanometer sheet, by
Figure is it can be seen that the unformed Ni (OH) prepared2Nanometer sheet is grown in calcium silicate nanowire surface, the size of nanometer sheet 50~
100nm or so, and be distributed than more uniform.
Embodiment 3
1, the synthesis of hard calcium silicate nanowire
It weighs 0.2360g four water-calcium nitrates and nine water sodium metasilicate of 0.2840g is dissolved in respectively in 25mL ultra-pure waters, in room temperature
Under, calcium nitrate solution is added dropwise in sodium silicate solution, and continuous magnetic agitation, finally obtains white suspension；Then
Obtained white suspension is transferred in being reacted in Teflon stainless steel high temperature reaction kettles, 200 DEG C are reacted for 24 hours, obtained production
Object water and ethyl alcohol are washed 3 times respectively, and then freeze drying example, obtains white powder.
2, hard calcium silicate nanowire induction prepares unformed Zn (OH)2Nanometer sheet
The hard calcium silicates white powder of preparation is configured to the hard calcium silicate nanowire dispersion liquid of 0.1wt%, by 3mmol's
Six water zinc chloride are added to the hard calcium silicate nanowire of 50mL and adhere to separately in liquid, and wherein metal ion or metal ion mixture be most
Final concentration of 0.06mol/L, magnetic agitation 0.5h are until solution went clear, 80 DEG C of water-bath 3h, room temperature cooling, the production of acquisition
Object is washed with water 3 times, and ethyl alcohol is washed 1 time, the dry 6h in 60 DEG C of vacuum drying chambers.
Unformed Zn (OH) prepared by the embodiment of the present invention 32Nanometer sheet is characterized.
Referring to Fig. 5, Fig. 5 is unformed Zn (OH) prepared by the embodiment of the present invention 32The stereoscan photograph of nanometer sheet, by
Figure is it can be seen that the Zn (OH) prepared2For nanometer chip size in 100nm or so, form is uniform.
Embodiment 4
1, the synthesis of hard calcium silicate nanowire
It weighs 0.2360g four water-calcium nitrates and nine water sodium metasilicate of 0.2840g is dissolved in respectively in 25mL ultra-pure waters, in room temperature
Under, calcium nitrate solution is added dropwise in sodium silicate solution, and continuous magnetic agitation, finally obtains white suspension；Then
Obtained white suspension is transferred in being reacted in Teflon stainless steel high temperature reaction kettles, 200 DEG C are reacted for 24 hours, obtained production
Object water and ethyl alcohol are washed 3 times respectively, and then freeze drying example, obtains white powder.
2, hard calcium silicate nanowire induction prepares unformed Co0.5Ni0.5(OH)2Nanometer sheet
The hard calcium silicates white powder of preparation is configured to the hard calcium silicate nanowire dispersion liquid of 0.1wt%, by 3mmol's
CoCL2 6H2O and six water nickel chlorides, which are added to the hard calcium silicate nanowire of 50mL, to be adhered to separately in liquid, wherein metal ion or metal from
The ultimate density of sub- mixture is 0.06mol/L, and magnetic agitation 0.5h is until solution went clear, 80 DEG C of water-bath 3h, room temperature
Cooling, the product of acquisition is washed with water 3 times, and ethyl alcohol is washed 1 time, the dry 6h in 60 DEG C of vacuum drying chambers.
Unformed Co prepared by the embodiment of the present invention 40.5Ni0.5(OH)2Nanometer sheet is characterized.
Referring to Fig. 6, Fig. 6 is unformed Co prepared by the embodiment of the present invention 40.5Ni0.5(OH)2The scanning electron microscope of nanometer sheet is shone
Piece, the Co prepared as seen from the figure0.5Ni0.5(OH)2Nanometer sheet is grown in calcium silicate nanowire surface, and the size of nanometer sheet exists
50~100nm or so, and be distributed than more uniform.
3, the preparation of cobalt nickel phosphide nanometer sheet
Weigh the Co of 100mg dihydrogen phosphites and sodium 10mg0.5Ni0.5(OH)2Nanometer sheet powder is individually placed to small porcelain boat
Head and tail.Small porcelain boat is placed in quartz ampoule, is passed through argon gas, sodium dihydrogen phosphite is close to air inlet, with the heating of 0.5 DEG C/min
Temperature is raised to 300 DEG C, constant temperature 3h by rate, after cooled to room temperature, obtains nickel cobalt phosphide nanometer sheet.
The nickel cobalt phosphide nanometer sheet prepared to the embodiment of the present invention 4 characterizes.
It is the transmission electron microscope photo of nickel cobalt phosphide nanometer sheet prepared by the embodiment of the present invention 4, Fig. 8 referring to Fig. 7-9, Fig. 7
For the stereoscan photograph of nickel cobalt phosphide nanometer sheet prepared by the embodiment of the present invention 4, the nickel cobalt phosphorus prepared as seen from the figure
Compound nanometer sheet is grown in calcium silicate nanowire surface, and the size of nanometer sheet is distributed more equal in 50~100nm or so
One, pattern does not change after phosphatization.Fig. 9 is the nickel cobalt phosphide nanometer sheet of the preparation of the embodiment of the present invention 4 in 0.5mol/
Evolving hydrogen reaction LSV curves in L sulfuric acid electrolytes, it can be seen that the nickel cobalt phosphide prepared has good evolving hydrogen reaction
HER properties, in 10mAcm-2Under current density, overpotential 105mV.
Embodiment 5
1, the synthesis of hard calcium silicate nanowire
It weighs 0.2360g four water-calcium nitrates and nine water sodium metasilicate of 0.2840g is dissolved in respectively in 25mL ultra-pure waters, in room temperature
Under, calcium nitrate solution is added dropwise in sodium silicate solution, and continuous magnetic agitation, finally obtains white suspension；Then
Obtained white suspension is transferred in being reacted in Teflon stainless steel high temperature reaction kettles, 200 DEG C are reacted for 24 hours, obtained production
Object water and ethyl alcohol are washed 3 times respectively, and then freeze drying example, obtains white powder.
2, hard calcium silicate nanowire induction prepares unformed Co0.33Ni0.33Mn0.33(OH)2Nanometer sheet
The hard calcium silicates white powder of preparation is configured to the hard calcium silicate nanowire dispersion liquid of 0.1wt%, by 3mmol's
CoCL2 6H2O and six water nickel chlorides, which are added to the hard calcium silicate nanowire of 50mL, to be adhered to separately in liquid, wherein metal ion or metal from
The ultimate density of sub- mixture is 0.06mol/L, and magnetic agitation 0.5h is until solution went clear, 80 DEG C of water-bath 3h, room temperature
Cooling, the product of acquisition is washed with water 3 times, and ethyl alcohol is washed 1 time, the dry 6h in 60 DEG C of vacuum drying chambers.
Unformed Co prepared by the embodiment of the present invention 50.33Ni0.33Mn0.33(OH)2Nanometer sheet is characterized.
Referring to Figure 10, Figure 10 is unformed Co prepared by the embodiment of the present invention 60.33Ni0.33Mn0.33(OH)2Nanometer sheet is swept
Electromicroscopic photograph is retouched, the unformed Co prepared as seen from the figure0.33Ni0.33Mn0.33(OH)2Nanometer sheet is grown in calcium silicates nanometer
Line surface, the size of nanometer sheet are distributed in 50~100nm or so than more uniform.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of unformed metal hydroxides nanometer sheet, which is characterized in that include the following steps：
A) aqueous dispersions of calcium silicate nanowire and soluble metal source compound are mixed, obtain mixed solution；
B the mixed solution) is subjected to water-bath, obtains unformed metal hydroxides nanometer sheet.
2. a kind of preparation method of phosphide nanometer sheet, which is characterized in that include the following steps：
A) aqueous dispersions of calcium silicate nanowire and soluble metal source compound are mixed, obtain mixed solution；
B) mixed solution is subjected to water-bath, obtains unformed metal hydroxides nanometer sheet；
C) by the unformed metal hydroxides nanometer sheet and dihydrogen phosphite salt, progress high temperature is forged under the conditions of protective atmosphere
It burns, obtains phosphide nanometer sheet.
3. preparation method according to claim 1 or 2, which is characterized in that the calcium silicate nanowire is as follows
It is prepared：
I) aqueous solution of soluble calcium salt is mixed with mensuration dissolubility silicic saline solution, is reacted, obtain suspension；
Ii the suspension) is subjected to heating reaction in confined conditions, obtains reaction product；
Iii it is freeze-dried after) washing the reaction product, obtains calcium silicate nanowire powder.
4. preparation method according to claim 3, which is characterized in that the soluble calcium salt is selected from calcium nitrate and calcium halide
In it is one or more；A concentration of 0.1~1.0mol/L of the aqueous solution of the soluble calcium salt；
The soluble silicate is selected from sodium metasilicate, a concentration of 0.1~1.0mol/L of the mensuration dissolubility silicic saline solution；
The molar ratio of calcium in the soluble calcium salt and the silicon in the soluble silicate is (0.1~10)：1.
5. preparation method according to claim 3, which is characterized in that in step i), time of the mixing is 0.5~
5h；
Step ii) in, the temperature of the heating reaction is 100~220 DEG C, and the reaction time is 1~30h；
Step iii) in, it washs to be washed respectively using water and ethyl alcohol, uses water washing number for 1~5 time, using ethyl alcohol
The number of washing is 1~5 time.
6. preparation method according to claim 1 or 2, which is characterized in that the aqueous dispersions of the calcium silicate nanowire
Mass fraction is 0.01wt%~10wt%；Wherein, what is mixed in the aqueous dispersions of the calcium silicate nanowire of every 20~200ml can
The amount of solube metallic source compound is 1.0mmol~10.0mmol.
7. preparation method according to claim 1 or 2, which is characterized in that the bath temperature is 20~100 DEG C, water-bath
Time be 1~for 24 hours.
8. preparation method according to claim 1 or 2, which is characterized in that the soluble metal source compound is selected from can
Solube metallic nitrate, soluble metal halide, soluble metal sulfate and one kind in soluble metal acetate or
It is a variety of；
Metallic element in the soluble metal source compound includes group VIII metal element, IV B races metallic element, V B races
It is one or more in metallic element, VI B races metallic element, VII B race's metallic elements and Group IIB metal element.
9. preparation method according to claim 2, which is characterized in that the dihydrogen phosphite salt is selected from sodium dihydrogen phosphite
Or potassium dihydrogen phosphite, the mass ratio of the unformed metal hydroxides nanometer sheet and dihydrogen phosphite salt is (10~500)：
(1~100).
10. preparation method according to claim 2, which is characterized in that the protective atmosphere condition is selected from nitrogen or argon gas,
The temperature of the high-temperature calcination is 100~900 DEG C, and the time is 1~10h, and calcining heating rate is 0.1~10 DEG C/min.
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| CN116618080A (en) * | 2023-07-24 | 2023-08-22 | 河南理工大学鄂尔多斯煤炭清洁开发利用研究院 | Preparation method of ammonia borane hydrolysis hydrogen evolution catalyst based on high-efficiency difunctional active site |
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